Cationic fluorinated ether silane compositions and related methods

ABSTRACT

Compositions comprising cationic compounds having fluorinated ether groups and silane groups are provided, the compounds having the formula (I).

TECHNICAL FIELD

The present disclosure relates to compositions comprising cationiccompounds having perfluorinated ether groups and reactive silane groups.More particularly, it relates to aqueous compositions comprisingcationic compounds having perfluorinated ether groups and reactivesilane groups, and methods for their use in protecting substrates.

BACKGROUND

Some fluorinated compounds have been shown to impart water repellency,oil repellency, or both to substrates such as, for example, textiles,paper, non-woven materials, leather, and masonry. Textiles have includednatural fibers such as cotton, and synthetic fibers such as polyester.Paper substrates have included paper used for packaging food. Repellencyhas been achieved by applying a composition comprising a fluorinatedcompound to, for example, the surface of a substrate. In many cases, afluorinated compound has been applied to the surface of a substrate in acomposition comprising a substantial amount of an organic solvent. Insome cases, the organic solvent has been flammable or combustible. Insome cases, the organic solvent has comprised halogen-containing speciessuch as tetrachloroethylene or trichlorotrifluoroethane. Methods toapply a composition comprising a fluorinated compound to a substratehave included spraying the solution from a pressurized container such asan aerosol can.

In many cases, compositions of fluorinated compounds have comprisedorganic, including halogen-containing, solvents, because the fluorinatedcompounds have had limited solubility in other solvents. However, forvarious reasons, there is awareness that the use of compositionscomprising substantial amounts of flammable or combustible organicsolvents may be less desirable. Similarly, there is awareness that theuse of compositions comprising substantial amounts of halogen-containingsolvents may be less desirable.

SUMMARY

We recognize that it has heretofore been difficult to developcompositions comprising fluorinated compounds and desirable solvents toimpart, for example, water repellency, oil repellency, or both to asubstrate. Thus, there is a need for compositions comprising fluorinatedcompounds, particularly cationic fluorinated compounds, that comprise orcan be delivered from aqueous or substantially aqueous media and thatcan impart water and oil repellency to substrates and, moreparticularly, to surfaces of substrates.

In one aspect, the present invention provides a composition comprisingat least one compound of Formula I:

wherein a, b, and c are each independently an integer from about 1 toabout 3; R_(f) is a perfluorinated ether group; A is a linking grouphaving the formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g areindependently integers from about 0 to about 10 and Z is selected fromthe group consisting of a covalent bond, a carbonyl group, a sulfonylgroup, a carboxamido group, a sulfonamido group, an iminocarbonyl group,an iminosulfonyl group, an oxycarbonyl group, a urea group, a urethanegroup, a carbonate group, and a carbonyloxy group; Y is a bridging grouphaving about 1 to about 10 carbon atoms, a valency from about 2 to about6, and comprising at least one of an alkylene group or an arylene group;Q is a connecting group having about 1 to about 10 carbon atoms, avalency from about 2 to about 6, and comprising at least one of analkylene group or an arylene group; R¹ and R² are independently selectedfrom the group consisting of a hydrogen atom, an alkyl group, an arylgroup, and an aralkyl group; each R³ is independently selected from thegroup consisting of hydroxy groups, alkoxy groups, acyl groups, acyloxygroups, halo groups, and polyether groups; and X⁻ is a counter ionselected from the group consisting of inorganic anions, organic anions,and combinations thereof.

In some embodiments, the present invention provides a compositioncomprising at least one compound of Formula II:

wherein n is an integer from about 2 to about 12; p is an integer fromabout 1 to about 6; b and c are each independently an integer from about1 to about 3; A is a linking group having the formula—C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integersfrom about 0 to about 10 and Z is selected from the group consisting ofa covalent bond, a carbonyl group, a sulfonyl group, a carboxamidogroup, a sulfonamido group, an iminocarbonyl group, an iminosulfonylgroup, an oxycarbonyl group, a urea group, a urethane group, a carbonategroup, and a carbonyloxy group; Y is a bridging group comprising analkylene group having about 1 to about 6 carbon atoms; Q is a connectinggroup comprising an alkylene group having about 1 to about 6 carbonatoms; R¹ and R² are independently alkyl groups having about 1 to about4 carbon atoms; each R³ is independently selected from the groupconsisting of hydroxy groups, methoxy groups, ethoxy groups, acetoxygroups, chloro groups, and polyether groups; and X⁻ is a counter ionselected from the group consisting of a halide, sulfate, phosphate, analkanoate, an alkyl sulfonate, an aryl sulfonate, an alkyl phosphonate,an aryl phosphonate, a fluorinated alkanoate, a fluorinated alkylsulfonate, a fluorinated aryl sulfonate, a fluorinated alkylsulfonimide, a fluorinated alkyl methide, and combinations thereof.

The compositions of the invention are useful for protecting a substrate,including imparting water repellency, oil repellency, or both to asubstrate. In particular, compositions of the invention are useful forimparting water repellency, oil repellency, or both to at least onesurface of a substrate. The compositions of the invention may be graftedor blended to a nanoparticle containing a functional group compatiblewith the silane group. In one aspect, the nanoparticle includes ahydroxyl functional group. In one aspect, the nanoparticle is a silica,titanium, or zirconium nanoparticle.

In another aspect, the present invention provides a method of protectinga surface, the method comprising 1) providing a composition comprising acompound of Formula I or Formula II, and 2) contacting a substrate withthe composition. In one aspect, the composition may be grafted orblended to a nanoparticle containing a functional group compatible withthe silane group of Formula I or Formula II prior to contact with asubstrate. The substrate may include ceramic, textile, silicate, paper,metal, wood, and plastic.

In another aspect, the present invention provides a kit comprising a) acomposition comprising a compound of Formula I, and b) instructions forusing the kit.

This summary is not intended to describe each and every embodiment orimplementation of the present invention. Further embodiments, features,and advantages of the present invention will be apparent from thefollowing detailed description thereof and from the claims.

DETAILED DESCRIPTION

In several places throughout the application, guidance is providedthrough lists of examples, which examples can be used in variouscombinations. In each instance, the recited list serves only as arepresentative group and should not be interpreted as an exclusive list.

As used herein,

Any recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, 5, etc.);

The terms “a,” “an,” “the,” “at least one,” and “one or more” are usedinterchangeably. Thus, for example, a composition that comprises “a”compound of Formula I can be interpreted to mean that the compositionincludes “one or more” compounds of Formula I; The term “perfluorinatedether group” refers to an ether group having at least onefluorine-to-carbon bond and being substantially free ofhydrogen-to-carbon bonds;

The term “perfluoropolyether group” refers to a perfluorinated ethergroup comprising more than one perfluorinated ether group;

The term “perfluoroalkyl group” refers to an alkyl group having at leastone fluorine-to-carbon bond and being substantially free ofhydrogen-to-carbon bonds; and

The term “perfluoroalkylene group” refers to an alkylene group having atleast one fluorine-to-carbon bond and being substantially free ofhydrogen-to-carbon bonds.

In one aspect, the present invention provides a composition comprisingat least one compound of Formula I:

Perfluorinated Ether Group R_(f)

The monovalent perfluorinated ether group comprises at least 1 carbonatom. The perfluorinated ether group may be a linear perfluorinatedether group, or it may comprise branched or cyclic structures. An oxygenatom in the perfluorinated ether group may be in one or more linear,branched, or cyclic structures. The perfluorinated ether group may havea weight average molecular weight of about 200 to about 7000, about 500to about 5000, about 1000 to about 5000, about 1000 to about 4000, about1000 to about 3000, or about 1000 to 1500. In some embodiments, theperfluorinated ether group has a weight average molecular weight ofabout 300, about 400, about 600, about 800, about 1000, about 1200,about 1400, about 1600, about 1800, about 2000, about 2200, about 2400,about 2600, about 2800, or about 3000.

The perfluorinated ether group may comprise a perfluoroalkyl group, aperfluoroalkylene group, or both. The perfluoroalkyl group may compriselinear, branched, or cyclic structures, or a combination of suchstructures. In some embodiments, the perfluoroalkyl group comprises morethan one of a linear, branched, or cyclic structure. Non limitingexamples of perfluoroalkyl groups include perfluoromethyl,perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoro-2-butyl,perfluorohexyl, and perfluorocyclohexyl, perfluorocyclohexylmethylgroups. The perfluoroalkylene group may comprise linear, branched, orcyclic structures, or a combination of such structures. In someembodiments, the perfluoroalkylene group comprises more than one of alinear, branched, or cyclic structure. Non limiting examples ofperfluoroalkylene groups include perfluoromethylene, perfluoroethylene,and perfluoro-1,2-propylene.

In some embodiments, the perfluorinated ether group is aperfluoropolyether group comprising at least two oxygen atoms.

The perfluorinated ether group may comprise a structureF(C_(m)F_(2m)O)_(n)C_(p)F_(2p)—, wherein m is an integer of at leastabout 1, n is an integer of at least about 2, and p is an integer of atleast about 1. It is understood that the preparation of perfluorinatedethers comprising such structures may result in a mixture ofperfluorinated ethers, each comprising structures having differentinteger values of m, n, and p. Such mixtures of perfluorinated ethersmay have non-integer average values of m, n and p. In some embodiments,m is an integer from about 1 to about 12, n is an integer from about 2to about 10, and p is an integer from about 1 to about 6. In someembodiments, m is an integer greater than about 2, greater than about 4,greater than about 6, greater than about 8, or greater than about 10. Insome embodiments, n is an integer greater than about 2. In someembodiments, n is an integer greater than about 3, greater than about 4,greater than about 5, greater than about 6, greater than about 7,greater than about 8, or greater than about 9. In some embodiments, p isan integer from about 1 to about 10, about 1 to about 8, or about 1 toabout 6. In some embodiments, p is an integer of 1, 2, 3, 4, 5, 6, 7, 8,9, or 10. The substructures —C_(m)F_(2m)— and —C_(p)F_(2p)— mayindependently comprise one or more of a linear, branched, or cyclicstructure.

The perfluorinated ether group may comprise a structureF(CF(CF₃)CF₂O)_(q)CF(CF₃)—, wherein q is an integer greater thanabout 1. It is understood that the preparation of perfluorinated etherscomprising such structures may result in a mixture of perfluorinatedethers each comprising structures having different integer value of q.Such mixtures of perfluorinated ethers may have non-integer averagevalues of q. In some embodiments, q is an integer greater than about 2,greater than about 3, greater than about 4, greater than about 5,greater than about 6, greater than about 7, greater than about 8,greater than about 9, greater than about 10, greater than about 15,greater than about 20, or greater than about 25. In some embodiments, qis an integer from about 2 to about 12. The perfluorinated ether groupmay be derived from, for example, tetrafluoroethylene orhexafluoropropylene, as described in, for example, U.S. Pat. Nos.3,882,193 (Rice, et al.) and 3,250,807 (Fritz et al.). Theperfluorinated ether group may be derived from, for example,hexafluoropropylene oxide, as described in, for example, U.S. Pat. Nos.6,923,921 (Flynn, et al.) and 3,250,808 (Moore, Jr., et al.).

Linking Group A

Linking group A links the perfluorinated ether group R_(f) to thebridging group Y. Linking group A has a valency at least sufficient tolink the perfluorinated ether group R_(f) to the bridging group Y. Insome embodiments, linking group A has a valency of at least about 2. Insome embodiments, linking group A has a valency of about 2. In someembodiments, linking group A has a valency from about 2 to about 6.

Linking group A may be formed as part of the perfluorinated ether groupR_(f), i.e., linking group A may be linked to perfluorinated ether groupR_(f) before it is linked to bridging group Y. Alternatively, linkinggroup A may be formed as part of bridging group Y and may be linked tobridging group Y before it is linked to perfluorinated ether groupR_(f). Alternatively, linking group A may be formed during a chemicalreaction of a perfluorinated ether precursor compound and a bridginggroup Y precursor compound. In this embodiment, linking group A may belinked to perfluorinated ether group R_(f) and bridging group Yessentially at the same time. In some embodiments, linking group A maybe divalent.

In some embodiments, the linking group A may have the formula—C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integersfrom about 0 to about 10 and subgroup Z is selected from the groupconsisting of a covalent bond, a carbonyl group, a sulfonyl group, acarboxamido group, a sulfonamido group, an iminocarbonyl group, animinosulfonyl group, an oxycarbonyl group, a urea group, a urethanegroup, a carbonate group, and a carbonyloxy group. In some embodiments,d and g are independently integers from about 1 to about 4, and Z isselected from the group consisting of a covalent bond, a carbonyl group,a sulfonyl group, a carboxamido group, a sulfonamido group, animinocarbonyl group, an iminosulfonyl group, an oxycarbonyl group, aurea group, a urethane group, a carbonate group, and a carbonyloxygroup. In some embodiments, for example when d and g are both zero,linking group A is comprises subgroup Z.

In some embodiments, for example when Z is a covalent bond, linkinggroup A comprises an alkylene group. The alkylene group may compriselinear, branched, or cyclic structures. The alkylene group may furthercomprise at least one heteroatom, e.g., oxygen, nitrogen, or sulfur. Thealkylene group may comprise at least about 1 carbon atom, or up to about2, up to about 3, up to about 4, up to about 5, up to about 6, up toabout 7, up to about 8, up to about 9, up to about 10, up to about 14,up to about 16, up to about 18, or up to about 20 carbon atoms.Non-limiting examples of alkylene groups include methylene, ethylene,1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4-cyclohexylene, and1,4-cyclohexyldimethylene.

In some embodiments, linking group A further comprises an arylene group.The arylene group comprises one or more aromatic rings. When the arylenegroup comprises more than one aromatic ring, the aromatic rings (whichmay be the same or different) may be fused, joined by a covalent bond,or joined via, for example, a joining group such as an alkylene group ora heteroatom such as oxygen. The arylene group may comprise at least oneheteroatom, e.g., oxygen, nitrogen, or sulfur. The arylene group maycomprise at least about 4 carbon atoms, or at least about 5, at leastabout 6, at least about 10, or at least about 14 carbon atoms.Non-limiting examples of arylene groups include phenyl, 1-naphthyl,2-naphthyl, 9-anthracenyl, furanyl, and thiophenyl.

In some embodiments, linking group A may comprise an aralkylene group.In some embodiments, linking group A may comprise an alkarylene group.

Bridging Group Y

Bridging group Y bridges the linking group A and the cationic nitrogenatom. Bridging group Y has a valency at least sufficient to bridge thelinking group A and the cationic nitrogen atom. As shown in Formulae Iand II, for example, bridging group Y may have a valency of at leastabout a+b. In some embodiments, bridging group Y has a valency of about2. In some embodiments, bridging group Y has a valency of greater thanabout 2. In some embodiments, bridging group Y has a valency from about2 to about 6. Bridging group Y may have a valency from about 2 to about6, may comprise about 1 to about 10 carbon atoms, and may comprise atleast one of an alkylene group or an arylene group.

Bridging group Y may be formed as part of a group comprising thecationic nitrogen atom. Alternatively, it may be formed as part of agroup comprising a nitrogen atom that will be later quaternized to formthe cationic nitrogen atom. Alternatively, it may be formed during achemical reaction of a linking group A precursor compound and a nitrogencontaining compound. In this embodiment, bridging group Y may bridgelinking group A and a neutral or cationic nitrogen atom essentially atthe same time. In some embodiments, bridging group Y may be divalent.

In some embodiments, bridging group Y comprises an alkylene group. Thealkylene group may comprise linear, branched, or cyclic structures. Thealkylene group may comprise at least one heteroatom, e.g., oxygen,nitrogen, or sulfur. The alkylene group may comprise at least about 1carbon atom, or up to about 2, up to about 3, up to about 4, up to about5, up to about 6, up to about 7, up to about 8, up to about 9, up toabout 10, up to about 14, up to about 16, up to about 18, or up to about20 carbon atoms. The alkylene group may comprise more than about 20carbon atoms. Non-limiting examples of alkylene groups includemethylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene,1,4-cyclohexylene, and 1,4-cyclohexyldimethylene.

In some embodiments, bridging group Y comprises an arylene group. Thearylene group comprises one or more aromatic rings. When the arylenegroup comprises more than one aromatic ring, the aromatic rings (whichmay be the same or different) may be fused, joined by a covalent bond,or joined via, for example, a joining group such as an alkylene group ora heteroatom such as oxygen. The arylene group may comprise at least oneheteroatom, e.g., oxygen, nitrogen, or sulfur. The arylene group maycomprise at least about 4 carbon atoms, or at least about 5, at leastabout 6, at least about 10, or at least about 14 carbon atoms.Non-limiting examples of arylene groups include phenyl, 1-naphthyl,2-naphthyl, 9-anthracenyl, furanyl, and thiophenyl.

In some embodiments, bridging group Y comprises an aralkylene group oran alkarylene group. The aralkylene or alkarylene group may comprise oneor more aromatic rings. When the aralkylene or alkarylene groupcomprises more than one aromatic ring, the aromatic rings (which may bethe same or different) may be fused, joined by a covalent bond, orjoined via, for example, a joining group such as an alkylene group or aheteroatom such as oxygen. The aralkylene or alkarylene group maycomprise at least one heteroatom, e.g., oxygen, nitrogen, or sulfur. Thearalkylene or alkarylene group may comprise at least about 4 carbonatoms, or at least about 5, at least about 6, at least about 10, or atleast about 14 carbon atoms.

Connecting Group Q

Connecting group Q connects the cationic nitrogen atom to the siliconatom.

Connecting group Q has a valency at least sufficient to connect thecationic nitrogen atom to the silicon atom. As shown in Formulae I andII, for example, connecting group Q has a valency of at least about c+1.In some embodiments, connecting group Q has a valency of about 2. Insome embodiments, connecting group Q has a valency of greater than about2. In some embodiments, connecting group Q has a valency from about 2 toabout 6. Connecting group Q may have a valency from about 2 to about 6,may comprise about 1 to about 10 carbon atoms, and may comprise at leastone of an alkylene group or an arylene group.

Connecting group Q may be formed as part of a group comprising thecationic nitrogen atom. Alternatively, it may be formed as part of agroup comprising a silicon atom. Alternatively, it may be formed duringa chemical reaction of a nitrogen containing compound and a siliconcontaining compound. In this embodiment, connecting group Q connects aneutral or cationic nitrogen atom and a silicon atom essentially at thesame time. In some embodiments, connecting group Q may be divalent.

In some embodiments, connecting group Q comprises an alkylene group. Thealkylene group may comprise linear, branched, or cyclic structures. Thealkylene group may comprise at least one heteroatom, e.g., oxygen,nitrogen, or sulfur. The alkylene group may comprise at least about 1carbon atom, or up to about 2, up to about 3, up to about 4, up to about5, up to about 6, up to about 7, up to about 8, up to about 9, up toabout 10, up to about 14, up to about 16, up to about 18, or up to about20 carbon atoms. In some embodiments, connecting group Q comprises atleast one oxyalkylene group. In some embodiments, connecting group Qcomprises a poly(oxyalkylene) group, for example, a poly(oxyethylene)group. The alkylene group may comprise more than about 20 carbon atoms.Non-limiting examples of alkylene groups include methylene, ethylene,1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4-cyclohexylene, and1,4-cyclohexyldimethylene.

In some embodiments, connecting group Q comprises an arylene group. Thearylene group comprises one or more aromatic rings. When the arylenegroup comprises more than one aromatic ring, the aromatic rings (whichmay be the same or different) may be fused, joined by a covalent bond,or joined via, for example, a joining group such as an alkylene group ora heteroatom such as oxygen. The arylene group may comprise at least oneheteroatom, e.g., oxygen, nitrogen, or sulfur. The arylene group maycomprise at least about 4 carbon atoms, or at least about 5, at leastabout 6, at least about 10, or at least about 14 carbon atoms.Non-limiting examples of arylene groups include phenyl, 1-naphthyl,2-naphthyl, 9-anthracenyl, furanyl, and thiophenyl.

In some embodiments, connecting group Q comprises an aralkylene or analkarylene group. The aralkylene or alkarylene group may comprise one ormore aromatic rings. When the aralkylene or alkarylene group comprisesmore than one aromatic ring, the aromatic rings (which may be the sameor different) may be fused, joined by a covalent bond, or joined via,for example, a joining group such as an alkylene group or a heteroatomsuch as oxygen. The aralkylene or alkarylene group may comprise at leastone heteroatom, e.g., oxygen, nitrogen, or sulfur. The aralkylene oralkarylene group may comprise at least about 4 carbon atoms, or at leastabout 5, at least about 6, at least about 10, or at least about 14carbon atoms.

R¹, R², and R³

In the compounds of Formulae I and II, R¹ and R² are bonded to thecationic nitrogen atom. Each R¹ and R² may be independently selectedfrom the group consisting of a hydrogen atom, an alkyl group, an arylgroup and an aralkyl group.

When either or both of R¹ or R² is an alkyl group, the alkyl group maycomprise about 1 carbon atom, more than about 1 carbon atom, more thanabout 2 carbon atoms, more than about 4 carbons atoms, more than about 6carbon atoms, more than about 8 carbon atoms, more than about 10 carbonatoms, more than about 16 carbon atoms, or more than about 20 carbonatoms. In some embodiments, the alkyl group comprises 1 to 8 carbonatoms. In some embodiments, the alkyl group comprises a straight chainalkyl group. In other embodiments, the alkyl group comprises a branchedalkyl group. In still other embodiments, the alkyl group comprises acyclic alkyl group. When each of R¹ and R² comprises an alkyl group, R¹and R² may comprise the same alkyl group, or R¹ and R² may comprisedifferent alkyl groups. Non-limiting examples of alkyl groups includemethyl, ethyl, 1-propyl, iso-propyl, butyl, iso-butyl, sec-butyl,pentyl, iso-pentyl, neo-pentyl, hexyl, 2-ethylhexyl, octyl, decyl,undecyl, dodecyl, tetradecyl, pentadecyl, octadecyl, cyclohexyl,4-methylcyclohexyl, cyclohexylmethyl, cyclopenyl, and cyclooctyl.

When either or both of R¹ or R² is an aryl group, the aryl group maycomprise one arene ring or more than one arene ring. Arene rings maycomprise up to 6 carbon atoms, up to 8 carbon atoms, up to 10 carbonatoms, up to 12 carbon atoms, up to 14 carbon atoms, up to 16 carbonatoms, or up to 18 carbon atoms. Arene rings may comprise a heteroatom,for example, nitrogen, oxygen, or sulfur. If more than one arene ring ispresent in an aryl group, the arene rings may be fused together, or theymay be joined by a chemical bond. When each of R¹ and R² comprises anaryl group, R¹ and R² may comprise the same aryl group or different arylgroups. Non-limiting examples of aryl groups include substituted andunsubstituted phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, andbiphenyl.

When either or both of R¹ or R² are an aralkyl group, the aralkyl groupmay comprise one arene ring or more than one arene ring. The aralkylgroup may comprise up to 6 carbon atoms, up to 8 carbon atoms, up to 10carbon atoms, up to 12 carbon atoms, up to 14 carbon atoms, up to 16carbon atoms, up to 18 carbon atoms, or up to 20 carbon atoms. If morethan one arene ring is present in the aralkyl group, the arene rings maybe fused together, or they may be joined by a chemical bond. Arene ringsmay comprise a heteroatom, for example, nitrogen, oxygen, or sulfur.When each of R¹ and R² comprises an aralkyl group, R¹ and R² maycomprise the same aralkyl group, or R¹ and R² may comprise differentaralkyl groups. Non-limiting examples of aralkyl groups include benzyl,1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 2-naphthylethyl, and9-anthracenylmethyl.

In the compounds of Formulae I and II, each R³ is independently bondedto the silicon atom. In some embodiments, each R³ is independentlyselected from the group consisting of hydroxy groups, alkoxy groups,acyl groups, acyloxy groups, halo groups, and polyether groups. In someembodiments, at least one R³ is independently bonded to the silicon atomvia a hydrolyzable bond. In this context, “bonded via a hydrolyzablebond” refers to the reactivity of the R³-silicon bond with water, i.e.,to a bond that is capable of undergoing a hydrolysis reaction. In someembodiments, R³ is bonded to the silicon atom via a bond including acarbon atom, i.e., R³ comprises a carbon atom bonded to the siliconatom. In some embodiments, R³ is bonded to the silicon atom via a bondincluding an atom other than a carbon atom. In some embodiments, R³ isbonded to the silicon atom via a bond including an oxygen atom, i.e., R³comprises an oxygen atom bonded to the silicon atom. In someembodiments, R³ is bonded to the silicon atom via a bond including anitrogen atom, i.e., R³ comprises a nitrogen atom bonded to the siliconatom.

Each R³ may independently be a non-ionic group or an ionic group. Theionic group may be cationic, anionic, or zwitterionic. Non-limitingexamples of non-ionic groups include hydroxy, alkoxy, acyl, acyloxy,halo, and polyether groups. Alkoxy groups include, for example, methoxyand ethoxy groups. Halo groups include, for example, chloro, bromo, andiodo groups. Acyl groups include, for example, acetyl, propionyl, andbenzoyl groups. Acyloxy groups include, for example, acetoxy andpropionoxy groups. Polyether groups may comprise oxyalkylene groups, forexample groups having the formula (OC_(v)H_(2v)), where v is an integerfrom about 1 to about 6. Non-limiting examples of polyether groupscomprising oxyalkylene groups include poly(oxymethylene),poly(oxyethylene), and poly(oxybutylene) groups. In some embodiments,the polyether group comprises about 1 to about 200 oxyalkylene groups.In some embodiments, the polyether group comprises about 1 to about 5,about 1 to about 10, about 1 to about 20, about 1 to about 30, about 1to about 40, or about 1 to about 50 oxyalkylene groups.

Non-limiting examples of ionic groups include groups such as—OCH₂CH₂N⁺(CH₃)₃I⁻, —OCH₂CH₂N⁺(CH₃)₃Cl⁻, and—OCH₂CH₂N⁺(CH₃)₂CH₂CH₂CH₂SO₃ ⁻. In some embodiments, polyether groupscomprising more than one oxyalkylene group further comprises a cationicgroup (e.g., a group comprising a cationic nitrogen atom), an anionicgroup, or both a cationic group and an anionic group.

Counter Ion X⁻

Counter ion X⁻ may comprise an organic anion, an inorganic anion, or acombination of organic and inorganic anions. In some embodiments,counter ion X⁻ may result from a chemical reaction that forms thecationic nitrogen atom, for example a reaction between an amine and analkylating agent such as, for example, a chloroalkylsilane, that forms anitrogen to carbon bond and displaces a chloride ion. In someembodiments, counter ion X⁻ may result from the protonation of an aminewith an acid. Such a reaction can provide a cationic nitrogen atom andthe conjugate base of the acid (i.e., the counter ion X⁻). In someembodiments, counter ion X⁻ may result from an ion exchange reaction,e.g., a reaction in which one anion is exchanged for another.

In some embodiments, counter ion X⁻ may be selected from the groupconsisting of a halide (e.g., chloride, bromide, or iodide), sulfate,phosphate, an alkanoate (e.g., acetate or propionate), an alkylsulfonate, an aryl sulfonate (e.g., benzenesulfonate), an alkylphosphonate, an aryl phosphonate, a fluorinated alkanoate (e.g.,trifluoroacetate), a fluorinated alkyl sulfonate (e.g.,trifluormethanesulfonate), a fluorinated aryl sulfonate (e.g.,4-fluorophenylsulfonate), a fluorinated alkyl sulfonimide (e.g.,bis(trifluoromethylsulfonyl)imide, a fluorinated alkyl methide (e.g.,tris(trifluoromethylsulfonyl)methide, and combinations thereof.

Solvents

The compositions of the invention may comprise at least onewater-soluble organic solvent. The compositions of the invention maycomprise less than about 1 weight percent to more than about 99 weightpercent water-soluble organic solvent. The compositions may compriseless than about 1 weight percent, more than about 1 weight percent, morethan about 5 weight percent, more than about 10 weight percent, morethan about 20 weight percent, more than about 30 weight percent, morethan about 40 weight percent, more than about 50 weight percent, morethan about 60 weight percent, more than about 70 weight percent, morethan about 80 weight percent, more than about 90 weight percent, or morethan about 99 weight percent water soluble organic solvent.

The water-soluble organic solvent may be soluble in water in allproportions of organic solvent and water. The water-soluble organicsolvent may be soluble in water up to about 1 weight percent, up toabout 2 weight percent, up to about 5 weight percent, up to about 10weight percent, up to about, 20 weight percent, up to about 30 weightpercent, up to about 40 weight percent, up to about 50 weight percent,up to about 60 weight percent, up to about 70 weight percent, up toabout 80 weight percent, or up to about 90 weight percent organicsolvent in water. The water-soluble organic solvent may be soluble inwater up to more than about 90 weight percent organic solvent in water.Suitable organic solvents include ketones (e.g., acetone), ethers (e.g.,dimethoxyethane, tetrahydrofuran), esters (e.g., methyl acetate),carbonates (e.g., propylene carbonate), amides (e.g.,dimethylacetamide), sulfoxides (e.g., dimethylsulfoxide), sulfones(e.g., sulfolane), and alcohols (e.g., ethanol, isopropanol,n-propanol). In some embodiments, the water-soluble organic solventcomprises one or more of butoxyethanol, methoxyethanol, propylene glycolmonopropyl ether, and 1-methoxy-2-propanol. In some embodiments, thewater-soluble organic solvent comprises a solvent used to prepare acompound of Formula I or Formula II. In some embodiments, thewater-soluble comprises a solvent not used to prepare a compound ofFormula I or Formula II, for example a solvent that may be added to thecomposition. In some embodiments, the water-soluble organic solvent maybe added to the composition during a processing or formulation step, forexample during a solvent exchange process.

The composition of the invention may comprise water. Water may bepresent from less than about 1 to more than about 99 weight percent ofthe composition. In some embodiments, water is present at more thanabout 1 weight percent, or more than about 10, more than about 20, morethan about 30, more than about 40, more than about 50, more than about60, more than about 70, more than about 80, more than about 90, morethan about 95, more than about 97, more than about 98, or more thanabout 99 weight percent of the composition.

The composition of the invention may comprise water and a water-solubleorganic solvent. The weight ratio of water to water-soluble organicsolvent may be from less than 1 to 99 to more than 99 to 1. In someembodiments, the weight ratio of water to water-soluble organic solventcan be at least about 1 to about 99, about 2 to about 98, about 5 toabout 95, about 10 to about 90, about 15 to about 85, about 20 to about80, about 30 to about 70, about 40 to about 50, about 50 to about 50,about 60 to about 40, about 70 to about 30, about 80 to about 20, about90 to about 10, about 95 to about 5, about 98 to about 2, or about 99 toabout 1.

The concentration of a compound of Formula I or Formula II in a mixtureof water and a water soluble organic solvent may be less than about 99weight percent, less than about 90 weight percent, less than about 80weight percent, less than about 70 weight percent, less than about 60weight percent, less than about 50 weight percent, less than about 40weight percent, less than about 30 weight percent, less than about 20weight percent, or less than about 10 weight percent. In someembodiments, concentration of a compound of Formula I or Formula II in amixture of a water soluble organic solvent and water is less than about9, less than about 8, less than about 7, less than about 6, less thanabout 5, less than about 4, less than about 3, less than about 2, lessthan about 1, or less than about 0.5 weight percent. In variousembodiments, the weight ratio of water to water-soluble organic solventis more than about 90 to about 10, and the concentration of at least onecompound of Formula I or Formula II in a mixture of a water solubleorganic solvent and water is less than about 10 weight percent, lessthan about 6 weight percent, less than about 4 weight percent, less thanabout 2 weight percent, or less than about 1 weight percent.

Optional Additives

The compositions of the invention may comprise one or more additives.Such additives may include, for example, UV absorbers, buffering agents,fireproofing agents, antimicrobial agents (e.g., fungicidal agents), ormineral salts.

Stability

The compositions of the invention, particularly compositions comprisingwater, may exhibit stability at room temperature (i.e., at about 25° C.)for periods of up to one day, up to one week, up to two weeks, up tothree weeks, up to one month, up to three months, up to six months, upto one year, up to two years, or up to three years. The compositions mayexhibit such stability at temperatures up to 50° C. As used herein, theterm “stability” refers to a property of compositions of the invention,particularly compositions comprising water, to remain substantiallyphysically unchanged, i.e., free of, for example, substantialprecipitate or substantial gel, for periods of time. In someembodiments, stability may be assessed by visually observing a sample ofa composition for the formation of precipitate or gel over a period oftime, e.g., over a storage time. It is recognized that, as prepared,compositions of the invention may have a small amount of precipitate orgel, or both, but this small amount does not substantially increase overtime.

Method and Kit

The present invention provides a method of protecting a surface, themethod comprising 1) providing a composition comprising a compound ofFormula I, and 2) contacting a substrate with the composition. In oneaspect, the composition may be grafted or blended to a nanoparticlecontaining a functional group compatible with the silane group ofFormula I or Formula II prior to contact with a substrate. In oneaspect, the nanoparticle includes a hydroxyl functional group. In oneaspect, the nanoparticle is silica, titanium or zirconium nanoparticle.

The step of contacting may comprise immersing, spraying, brushing,rolling, flooding, or condensing. The substrate may include ceramic,textile, silicate, paper, metal, wood, and plastic. In some embodiments,the substrate may be cotton, viscose, wool, silk, polyester, polyamide,styrene polymers and copolymers, cellulose acetate, rayon, clay,ceramic, glass, concrete, and combinations thereof. In some embodiments,the method comprises contacting a substrate with a compositioncomprising at least one compound of Formula I or Formula II, at leastone water soluble organic solvent, and water.

The substrate may comprise ceramic. Such ceramic may be in the form of,for example glazed or unglazed ceramic tile (e.g., kitchen or bathroomtile). The substrate may comprise glass, for example fiberglass, flintglass or borosilicate glass. The substrate may comprise concrete,including, for example, structural concrete and decorative concrete. Insome embodiments, the substrate may be a textile comprising a blend ofcotton and polyester or a blend of polyamide and polyester. In someembodiments, the substrate comprises a textile such as for use inclothing or upholstery.

The step of contacting may be carried out at room temperature (i.e., atabout 25° C.) or at elevated temperature. In some embodiments, themethod comprises the step of heating the subtrate before contacting itwith a composition of the invention. In some embodiments, the methodcomprises the step of heating the substrate after contacting it with acomposition of the invention. Heating the substrate after contacting itwith a composition of the invention may increase the rate of evaporationof the solvents.

The compositions of the invention can be used to protect a substrate,particularly the surface of a substrate, so as to render the substratewater repellent, oil repellent, or both, or to provide soil and/or stainrepellency to the substrate. Protection of a substrate may result inrendering the protected substrate, particularly the protected surface ofa protected substrate, more readily cleanable due to the oil and/orwater repellent nature of the protected substrate or surface. In someembodiments, a substrate is protected by an amount of a compound ofFormula I or Formula II sufficient to result in the substrate having anadvancing contact angle with deionized or distilled water of at leastabout 70° and an advancing contact angle with hexadecane of at leastabout 40°. A compound of Formula I or Formula II may react with asubstrate to form an ionic or a covalent bond. In some embodiments,heating the substrate before or after contacting it with a compositionof the invention may facilitate a reaction between a compound and thesubstrate.

When, for example, the substrate is a textile, the textile or thesurface of the textile may be protected by an amount of a compound ofFormula I or Formula II sufficient to result in the textile havingrepellency to water and/or to oil. The desired degree of repellency towater and/or to oil may depend, for example, on the intended end use ofthe textile. In some embodiments, the surface of the textile may beprotected by an amount of a compound of Formula I or Formula IIsufficient to provide resistance to water that is sprayed onto thetextile, i.e., the protected textile can have a high “spray rating”value.

The method of protecting a surface may comprise combining a compositionof the invention, particularly a composition comprising a water-solubleorganic solvent, with water. A composition of the invention may becombined with water by adding water to the composition or by adding thecomposition to water. In some embodiments, the providing step comprisescombining the composition with water. In some embodiments, combining acomposition of the invention with water comprises diluting a compositionof the invention with water.

In some embodiments, a substrate, or particularly the surface of asubstrate, may be cleaned prior to contacting it with the composition ofthe invention. The substrate may be cleaned prior to contacting it withthe composition of the invention, for example by washing the substratewith water or with an organic solvent.

In another aspect, the present invention provides a kit comprising acomposition comprising a compound of Formula I. In some embodiments, thekit may comprise an applicator comprising a container, a sprayer, abrush, a roller, or combinations thereof. In some embodiments, the kitmay comprise instructions for using the kit. The instructions mayinclude instructions relating to, for example, combining a compositionwith water or diluting a composition with water. The instructions mayfurther include information relating to the selection of a method tocontact a substrate with a composition of the invention.

EXAMPLES

Unless otherwise noted, all solvents and reagents were or can beobtained from Sigma-Aldrich Corp., St. Louis, Mo.

Spray Rating (SR) Test Method

The spray rating of a treated substrate is a value indicative of thedynamic repellency of the treated substrate to water that impinges onthe treated substrate. The repellency was measured by Test Method22-1996, published in the 2001 Technical Manual of the AmericanAssociation of Textile Chemists and Colorists (AATCC), and was expressedin terms of a ‘spray rating’ (SR) of the tested substrate. The sprayrating was obtained by spraying 250 ml water on the substrate from aheight of 15 cm. The wetting pattern was visually rated using a 0 to 100scale, where 0 means complete wetting and 100 means no wetting at all.

Water Repellency (WR) Test Method

The water repellency (WR) of a substrate was measured using a series ofwater-isopropanol test liquids and was expressed in terms of the “WR”rating of the treated substrate. The WR rating corresponded to the mostpenetrating test liquid which did not penetrate or wet the substratesurface after 15 seconds exposure. Substrates which were penetrated byor were resistant only to 100% water (0% isopropanol), the leastpenetrating test liquid, were given a rating of 0, whereas substratesresistant to 100% isopropanol (0% water), the most penetrating testliquid, were given a rating of 10. Other intermediate ratings werecalculated by dividing the percent isopropanol in the test liquid by 10,e.g., a treated substrate resistant to a 70%/30% isopropanol/waterblend, but not to an 80%/20% blend, would be given a rating of 7.

Oil Repellency (OR) Test Method

The oil repellency of a substrate was measured by the AmericanAssociation of Textile Chemists and Colorists (AATCC) Standard TestMethod No. 118-1983, which test was based on the resistance of a treatedsubstrate to penetration by oils of varying surface tensions. Treatedsubstrates resistant only to Nujol® mineral oil (the least penetratingof the test oils) were given a rating of 1, whereas treated substratesresistant to n-heptane (the most penetrating of the test liquids) weregiven a rating of 8. Other intermediate values were determined by use ofother pure oils or mixtures of oils, as shown in Table 1.

TABLE 1 Test Liquids for Oil Repellency (OR) AATCC Oil Repellency RatingNumber Compositions 1 Nujol ® 2 Nujol ®/n-Hexadecane 65/35 3n-Hexadecane 4 n-Tetradecane 5 n-Dodecane 6 n-Decane 7 n-Octane 8n-Heptane

Example 1 Preparation of a Compound of Formula I

A 500 mL round bottom flask, fitted with a magnetic stir bar, wascharged with methyl ester terminated perfluoropolyether oligomer havinga weight average molecular weight of approximately 1285 grams per mole(100 g; prepared essentially as described in U.S. Pat. No. 3,250,808(Moore, Jr. et al.)), N,N-dimethylaminopropylamine (8.1 g), andtert-butyl methyl ether (100 g). The flask was fitted with a refluxcondenser, and the mixture was stirred and heated to reflux. Theprogress of the reaction was monitored using infrared spectrophotometry.After approximately 12 hours, the mixture was allowed to cool to roomtemperature and was then vacuum filtered. The volatile components wereremoved using a rotary evaporator to afford a reaction intermediate.

Then a 50 mL round bottom flask, fitted with a magnetic stir bar, wascharged with the reaction intermediate (1 g) and3-chloropropyltrimethoxysilane (0.148 g). The flask was fitted with areflux condenser, and the mixture was stirred and heated under anitrogen atmosphere to a temperature of approximately 140° C. Afterapproximately 12 hours, the mixture was allowed to cool to roomtemperature to afford the product. The ¹H NMR spectrum of the productwas consistent with the assigned structure.

Comparative Example 1 Preparation of a Fluoroaliphatic Ammonium SilaneCompound

A 500 mL 3-neck round bottom flask, fitted with a mechanical stirrer anda nitrogen inlet tube connected to a bubbler, was charged withC₆F₁₃CH₂CH₂OH (72.86 g; obtained from Clariant Corp., Mount Holly,N.C.), triethylamine (23.27 g), and tert-butyl methyl ether (121.29 g).The flask was cooled in an ice bath with the contents under a nitrogenatmosphere. The flask was fitted with an addition funnel, and thenmethanesulfonyl chloride (25.20 g) was added via the funnel overapproximately 120 minutes. The mixture was allowed to warm to roomtemperature overnight. The mixture was then washed with aqueous 1N HCl(120 g) and then with 2 weight percent aqueous sodium carbonate (120 g).The mixture was dried over anhydrous magnesium sulfate. The mixture wasthen filtered. Solvent removal using a rotary evaporator afforded anintermediate product as a solid.

A 50 mL round bottom flask, fitted with a magnetic stir bar, was chargedwith the intermediate product (1 g) and3-N,N-dimethylpropyltrimethoxysilane (0.4688 g). The mixture was stirredunder a nitrogen atmosphere and was heated to approximately 80° C. forapproximately 4 hours. The mixture was then allowed to cool to roomtemperature to afford the product.

Examples 2 and 3 Stability of Solutions

The stability of solutions of compositions comprising the products ofExample 1 and Comparative Example 1 was evaluated. For Example 2, 25milliliters of a solution of 1 weight percent of the product of Example1 in a mixture of 99 parts by weight water and 1 part by weightisopropanol in a screw-cap glass vial was stored in an oven at 65° C.

After one week, no gellation or precipitation was observed. After threeweeks, no gellation or precipitation was observed. For Example 3, 25milliliters of a solution of 1 weight percent of the product ofComparative Example 1 in water in a screw-cap glass vial was stored inan oven at 65° C. After one week, no gellation or precipitation wasobserved.

Examples 4-9

The oil repellency (OR), water repellency (WR), and spray rating (SR) ofthree fabrics sprayed with a solution of the compound of Example 1 weredetermined as described above. A 1 weight percent solution of thecompound of Example 1 in a 1 volume percent mixture of isopropanol inwater was sprayed onto each of a cotton fabric (style 400M, availablefrom Testfabrics, Inc., West Pittiston, Pa.), a 65/35 polyester/cottonblend fabric (style 7436, available from Testfabrics, Inc., WestPittiston, Pa.), and a khaki color cotton twill fabric (available fromAvondale Mills, Graniteville, S.C.) using an aerosol sprayer availableunder the trade designation PREVAL sprayer from Precision Valve Corp.,Yonkers, N.Y. The fabrics were sprayed with 10 to 12 grams of solutioneach. For Examples 4-6, the sprayed fabrics were allowed to dry in airat room temperature overnight. For Examples 7-9, the sprayed fabricswere dried using an iron (dry; highest temperature setting). The ironedfabrics were allowed to stand at room temperature overnight before theywere tested. The data are given in Table 2.

TABLE 2 Test Results for Examples 4-9. Example Fabric WR OR SR 4 400Mcotton 3 5 50 5 65/35 poly/cotton 3 5 50 6 cotton twill - khaki 0 4 0 7400M cotton 2 5 60 8 65/35 poly/cotton 3 5 60 9 cotton twill - khaki 0 50

Examples 10-11 and Comparative Examples 2-3

Two fabrics (Example 10 and Comparative Example 2, the 65/35polyester/cotton blend fabric; Example 11 and Comparative Example 3, the400M cotton fabric) were each padded with a solution prepared bydiluting a 50 weight percent solution of the compound of Example 1 inisopropanol with water (Examples 10-11) or with a solution prepared bydiluting a commercially available fabric protector (available under thetrade designation 3M PROTECTIVE CHEMICAL PM-930) with water to providecompositions that delivered 1.2 weight percent solids on fabric by padapplication. Each padded fabric was dried in air at room temperatureovernight. The oil repellency (OR), water repellency (WR), and sprayrating (SR) of the fabrics were determined as described above. The dataare given in Table 3.

TABLE 3 Test Results for Examples 10-11 and Comparative Examples 2-3.Example Fabric WR OR SR 10 65/35 poly/cotton 3 6 50 11 400M cotton 0 550 Comparative 2 65/35 poly/cotton 1 5 0 Comparative 3 400M cotton 0 5 0

Example 12 and Comparative Examples 4-6 Dynamic Contact AngleMeasurements

For each of Example 12 and Comparative Examples 4-5, two glass slides(each having a surface area of 19.35 square centimeters) were coatedwith a test solution. For Example 12, the glass slides were dipped intoa 1 weight percent solution of the compound of Example 1 in a 5 weightpercent solution of isopropanol in water. For Comparative Example 4, theglass slides were dipped into a 1 weight percent solution of thecompound of Comparative Example 1 in a 5 weight percent solution ofisopropanol in water. For Comparative Example 5, the glass slides weredipped into a fluoropolymer coating solution available under the tradedesignation 3M EASY CLEAN COATING ECC-1000 from 3M Company, St. Paul,Minn. For Comparative Example 6, an untreated glass slide was evaluated.Each glass slide was then rinsed with water and was allowed to dryovernight at room temperature. One set of glass slides (from each ofExample 12 and Comparative Examples 4-6) were scrubbed ten times with aheavy duty scouring pad (available under the trade designationSCOTCH-BRITE from 3M Company, St. Paul, Minn.). The dynamic contactangles of water (deionized and filtered) and hexadecane (reagent grade)were measured on each surface using a Model VCA-2500XE video contactangle analyzer (obtained from AST Products Inc., Billerica, Mass.). Thedata are given in Table 4. In Table 4, the term “Coating Material”refers to the coating composition on the glass, “H” refers tohexadecane, “W” refers to water, “adv” refers to advancing contactangle, and “rec” refers to receding contact angle. For example, “W-adv”refers to the water advancing contact angle.

TABLE 4 Contact Angle Data for Example 12 and Comparative Examples 4-6.Example Coating Material W-adv W-rec H-adv H-rec 12 Example 1 75° 48°68° 52° 12 (scrubbed) Example 1 73° 45° 62° 43° Comparative 4Comparative 1 97° 63° 54° 45° Comparative 4 Comparative 1 93° 47° 49°40° (scrubbed) Comparative 5 ECC-1000 82° 47° 63° 49° Comparative 5ECC-1000 80° 65° 55  49° (scrubbed) Comparative 6 none 0° 0°  0° 0°Comparative 6 none 0° 0°  0° 0° (scrubbed)

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1. A composition comprising at least one compound of Formula I:

wherein a, b, and c are independently integers from 1 to 3; R_(f) is aperfluorinated ether group; A is a linking group having the formula—C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independently integersfrom 0 to 10 and Z is selected from the group consisting of a covalentbond, a carbonyl group, a sulfonyl group, a carboxamido group, asulfonamido group, an iminocarbonyl group, an iminosulfonyl group, anoxycarbonyl group, a urea group, a urethane group, a carbonate group,and a carbonyloxy group; Y is a bridging group having 1 to 10 carbonatoms, a valency from 2 to 6, and comprising at least one of an alkylenegroup or an arylene group; Q is a connecting group having 1 to 10 carbonatoms, a valency from 2 to 6, and comprising at least one of an alkylenegroup or an arylene group; R¹ and R² are independently selected from thegroup consisting of a hydrogen atom, an alkyl group, an aryl group, andan aralkyl group; each R³ is independently selected from the groupconsisting of hydroxy groups, alkoxy groups, acyl groups, acyloxygroups, halo groups, and polyether groups; and X⁻ is a counter ionselected from the group consisting of inorganic anions, organic anions,and combinations thereof.
 2. The composition of claim 1 furthercomprising a water-soluble organic solvent.
 3. The composition of claim2 wherein the water-soluble organic solvent is selected from the groupconsisting of alcohols, ketones, and ethers.
 4. The composition of claim1 further comprising water.
 5. The composition of claim 1 wherein theperfluorinated ether group is a perfluoropolyether group.
 6. Thecomposition of claim 1 wherein the perfluorinated ether group has aweight average molecular weight of at least about
 1000. 7. Thecomposition of claim 1 wherein the counter ion X⁻ is selected from thegroup consisting of a halide, sulfate, phosphate, an alkanoate, an alkylsulfonate, an aryl sulfonate, an alkyl phosphonate, an aryl phosphonate,a fluorinated alkanoate, a fluorinated alkyl sulfonate, a fluorinatedaryl sulfonate, a fluorinated alkyl sulfonimide, a fluorinated alkylmethide, and combinations thereof.
 8. The composition of claim 1 whereinat least one of d or g is at least 1, and Z is a covalent bond.
 9. Thecomposition of claim 1 wherein the bridging group Y comprises analkylene group having 1 to 6 carbon atoms.
 10. The composition of claim1 wherein the connecting group Q comprises an alkylene group having 1 to6 carbon atoms.
 11. The composition of claim 1 wherein R¹ and R² areindependently a hydrogen atom or an alkyl group having 1 to 8 carbonatoms.
 12. The composition of claim 1 wherein the perfluorinated ethergroup has the structure F(C_(m)F_(2m)O)_(n)C_(p)F_(2p)—, wherein m is aninteger from 1 to 12, n is an integer from 2 to 10, and p is an integerfrom 1 to
 6. 13. The composition of claim 1 wherein the perfluorinatedether group has the structure F(CF(CF₃)CF₂O)_(q)CF(CF₃)—, wherein q isan integer from 2 to
 12. 14. The composition of claim 1 wherein thecomposition is in a form selected from the group consisting of a liquid,a solid, a solution, a foam, a dispersion, a suspension, and anemulsion.
 15. A composition comprising at least one compound of FormulaII

wherein n is an integer from 2 to 12; p is an integer from 1 to 6; b andc are independently integers from 1 to 3; A is a linking group havingthe formula —C_(d)H_(2d)ZC_(g)H_(2g)—, wherein d and g are independentlyintegers from 0 to 10 and Z is selected from the group consisting of acovalent bond, a carbonyl group, a sulfonyl group, a carboxamido group,a sulfonamido group, an iminocarbonyl group, an iminosulfonyl group, anoxycarbonyl group, a urea group, a urethane group, a carbonate group,and a carbonyloxy group; Y is a bridging group comprising an alkylenegroup having 1 to 6 carbon atoms; Q is a connecting group comprising analkylene group having 1 to 6 carbon atoms; R¹ and R² are independentlyalkyl groups having 1 to 4 carbon atoms; each R³ is independentlyselected from the group consisting of hydroxy groups, methoxy groups,ethoxy groups, acetoxy groups, chloro groups, and polyether groups; andX⁻ is a counterion selected from the group consisting of a halide,sulfate, phosphate, an alkanoate, an alkyl sulfonate, an aryl sulfonate,an alkyl phosphonate, an aryl phosphonate, a fluorinated alkanoate, afluorinated alkyl sulfonate, a fluorinated aryl sulfonate, a fluorinatedalkyl sulfonimide, a fluorinated alkyl methide, and combinationsthereof.
 16. The composition of claim 15 further comprising awater-soluble organic solvent.
 17. The composition of claim 16 whereinthe water-soluble organic solvent is selected from the group consistingof alcohols, ketones, and ethers.
 18. The composition of claim 15further comprising water.
 19. The composition of claim 1 or 15 wherein dand g are independently integers from one to four, and Z is selectedfrom the group consisting of a covalent bond, a carbonyl group, asulfonyl group, a carboxamido group, a sulfonamido group, a urea group,a urethane group, and a carbonyloxy group.
 20. The composition of claim1 or 15 wherein the bridging group Y comprises a propylene group, theconnecting group Q comprises a propylene group, b is 1, and c is
 1. 21.The composition of claim 1 or 15 wherein the composition is grafted orblended with a nanoparticle containing a functional group compatiblewith the silane group.
 22. A method of protecting a surface, the methodcomprising: 1) providing a composition according to claims 1; and 2)contacting a substrate with the composition.
 23. The method of claim 22wherein the providing step comprises combining the composition withwater.
 24. The method of claim 22 wherein the providing step furthercomprises grafting or blending the composition with a nanoparticlecontaining a functional group compatible with the silane group.
 25. Themethod of claim 22 wherein the substrate is selected from the groupconsisting of ceramic, textile, silicate, paper, metal, wood, andplastic.
 26. (canceled)